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sity and have ammonia-like odor. The EA freezing point is considerably decreased by adding water. MEA and DEA are soluble, with
any proportion, in water and alcohol but considerably less in ether.
All amines form white crystalline solids when freeze [7].
Very few quantitative studies have been conducted for EA synthesis. One source is the study conducted by Japanese researchers
[8], yet the lack of confirmed data renders it unsuitable to construct
further modeling and simulation based on a few kinetic data.
In Iran, EA is produced at Arak Petrochemical Complex (APC).
In this plant EA is produced from a direct reaction of EO and aqueous
ammonia solution in liquid phase (without addition of catalyst) in a
tubular fixed bed reactor. EO is also produced in the plant, whereas
the required ammonia is provided by the domestic petrochemical
industry. The annual APC production capacity of EA is 30,000 tons
consisting of 10,000 tons MEA, 8,000 tons TEA and the rest is DEA.
Purity of the produced MEA and DEA is 99%, while TEA is produced in 99% and 85% purities [6]. This paper aims to simulate
and investigate optimal operating condition of the MEA plant. Based
on our literature review no work has been done in this case regardless of the importance of MEA.
INTRODUCTION
Regarding the broad application of Ethanol Amine (EA), its production is of great interest to the petrochemical industry. The industrial production of EA was accomplished in 1930 followed by the
large-scale production in 1945, when alkoxylation with ethylene
oxide (EO) and propylene oxide was replaced by chlorohydrins [1,2].
The commercial importance of EA increased from 1970, when industrial production of EO began. The modern industrial production
of EA is operated exclusively by reaction of EO and excess amount
of ammonia in presence of water [3]. It has been proved that a
small amount of water is necessary to promote reaction. When there
is not any water in the system, EO does not react with ammonia.
In fact, water plays a catalytic role in the corresponding reactions
[2,4]. Based on operational conditions monoethanolamine (MEA),
diethanolamine (DEA) and triethanolamine (TEA) are produced
through three parallel-consecutive competitive reactions [1].
EAs react with a large number of compounds such as ammonia,
carbon dioxide, sulfuric acid, sodium hydroxide, carbon disulfide,
thionyl chloride and also with acids and aromatic aldehydes [4-6].
In general, they are very desirable as H2S and CO2 absorbents for
natural gas treatment [7]. Because of alcoholic characteristics, MEA
and DEA have broader industrial applications. On the other hand,
DEA and TEA are used in making detergents, textiles, pharmaceuticals, emulsifiers in drilling and excavation of oil wells, corrosion
inhibitors as well as additives to cement [2].
EAs are hygroscopic, colorless and viscous liquids at room temperature. TEA boils at 27 oC, whereas the other two EAs have higher
boiling points. Their densities are slightly greater than water den-
EA PROCESS DESCRIPTION
The commonly utilized process of EA production is the SRI process, which has been typically designed for producing 45,000 ton/
year EA from ammonia and EO, the production capacity that most
of the USA, Western Europe, and Japanese factories fall in. The
operational conditions of SRI process have been regulated to prohibit formation of any by-product. This designing concept, however,
is not employed in the industry, and the industrial applications differ from the SRI process in that the equipment and plant structure
are different, but the reaction is identical [1].
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Fig. 1. Simplified flow diagram of ethanol amine production plant (Adapted from [1]).
(2)
(3)
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G. Zahedi et al.
(4)
k0
14.6
15.7
15.1
12.7
4.111080
1.131010
2.941090
4.231060
Other relations were presented for the specific rate of contributing reactions as Eqs. (5) to (7) [8]:
11000
2
2
k1 = (41+ 4[ H2 O] ) 10 exp ------------------
RT
(5)
k2=(7.20.042[H2O])k1
(6)
k3=(160.22[H2O])k2
(7)
7.6
14500
exp ------------------
RT
(8)
(9)
d [EO ]
--------------- = k1 [NH3 ][ EO] k2[MEA ][EO] k3 [DEA ][EO]
dt
(10)
d [MEA ]
--------------------- = k1[NH3 ][EO] k2 [MEA][EO ]
dt
(11)
d [DEA ]
-------------------- = k2 [MEA][EO ] k3[DEA ][EO ]
dt
(12)
d [TEA ]
------------------- = k3[DEA] [EO]
dt
(13)
For the optimization, Matlab 7.6 with solver ODE23s [14] was used
to solve the series of above ordinary differential equations (ODEs).
Fig. 2 illustrates the proposed algorithm for obtaining kinetic constants. The algorithm first estimates the parameters (k1, k2, and k3),
followed by solving the ODEs and checking the error between results and the experimental data. The process continues until convergence to the experimental data is reached.
Results of the optimization of reaction rate constants are presented in Table 2.
PROCESS MODELING
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vestigate the effects of different parameters on the process and subsequent optimization of process operation. For the process modeling in this study Hysys 3.2 was used. Fig. 3 illustrates the process
flowchart made in Hysys, with the four reactors are labeled as R101A
to R101D.
Appropriate equations were selected in order to estimate the physical properties of all components in the system. The results of simulation are strongly influenced by the selected Hysys thermodynamic
model, i.e., selection of an inappropriate thermodynamic model will
result in error in model predictions. The thermodynamic models in the
Hysys environment are classified into three main groups: 1- equations
of state such as SRK; 2- equations of activity coefficient such as
NRTL; 3- special thermodynamic models such as the amine model
prepared for a system consisting of amines, acidic gas and water [15].
SIMULATION RESULTS
To build the process flow diagram in the Hysys environment,
the composition of materials, equation of state and reactions were
specified. The reactor feed specifications are presented in Table 3.
Table 4 provides a comparison between the simulation and process (SRI) data. For comparison, the errors in the simulation are
also given. Maximum error appears to be less than 4%, validating
the simulation approach.
For different towers Tables 5, 6 and 7 present the estimated pro-
The objective of mathematical modeling and simulation is to inTable 3. Characteristics of feed to the reactor
Table 2. Results of optimization algorithm for kinetic parameters
estimation
Reaction
EO+NH3
EO+MEA
EO+DEA
k0
19660
19660
19660
1.581107
04.92108
005.2108
Temperature (oC)
Pressure (KPa)
Total molar flow (kg mol/hr)
Molar flow of ammonia (kg mol/hr)
Molar flow of EO (kg mol/hr)
Molar flow water (kg mol/hr)
85
1.02104
687.83
529.09
105.82
052.92
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G. Zahedi et al.
SRI result
(kg/hr)
Hysys result
(kg/hr)
Percent of
relative error
Ammonia
EO
Water
MEA
DEA
TEA
7842
0935
2456
2037
1338
7864
0935
2365
1966
1388
0.28
0.00
3.69
3.47
3.72
SRI data
Hysys result
SRI result
Hysys result
SRI result
Hysys result
470.0
934.0
2456.60
2037.12
1338.73
0491.60
934.0
2366.33
1966.43
1479.61
0024.53
0934.21
2454.34
2037.12
1338.73
0024.49
0933.90
2366.33
1966.43
1479.61
0006.35
2444.36
2036.67
1338.73
0006.03
2354.10
1966.43
1388.91
SRI result
Hysys result
SRI result
Hysys result
SRI result
Hysys result
2426.22
0016.32
0000.45
2329.03
0015.29
0000.51
0018.14
2020.34
1338.28
0018.66
1966.42
1479.56
001.36
468.50
000.96
615.80
SRI result
Hysys result
SRI result
Hysys result
Hysys result
0018.14
1867.96
0006.35
0015.17
1541.75
0005.74
150.56
410.86
145.94
410.86
001.36
421.75
000.52
423.12
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Compound
Price ($/tonne)
Ammonia
EO
Water
MEA
DEA
TEA (%99)
TEA (%85)
025.25
155.26
018.00
177.40
193.95
190.92
187.19
tion in this part of study. As there was not any idea about a suitable
practical objective function, both of the objective functions were
examined. The GS method was first applied to optimize the molar
production of MEA as the objective function as follows:
Objective function (J)=MoleMEA
(14)
(15)
J=[kgMEApriceMEA+kgDEApriceDEA+kgTEA(%85)priceTEA(%85)
J=+kgTEA(%99) priceTEA(%99)][kgNH3priceNH +kgEOpriceEO
J=+kgH OpriceH O].
(16)
An EA production plant was simulated by using Hysys software. The results of simulation revealed that the simulated data have
a good agreement with the SRI data. There are, however, some errors
in the predicted data, mainly because of the softwares weakness in
this study, and particularly due to the available Hysys thermodynamic models.
The simulation also necessitates using accurate reaction rates.
Korean J. Chem. Eng.(Vol. 26, No. 6)
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G. Zahedi et al.
C
: concentration [%wt]
E
: activation energy [kcal mole1]
J
: objective function
k0
: frequency factor [L mol1 min1]
k1, k2, k3 : kinetics constants [L mol1 min1]
ODE : ordinary differential equation
R
: gas constant [kcal mol1 K1]
T
: temperature [K], or otherwise stated
t
: time [min]
Greek Letter
: error
REFERENCES
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